Metal alkyls and heterobimetallic dinitrogen and nitrido complexes

The Rh(III) methyl complexes Rh(mac)(Ch3)L (mac = 1,2-bis(2- pyridinecarboxamido)benzene (bpb) or tetra(p-tolyl)porphyrin dianion (TTP), octaethylporphyrin dianion (OEP); L = unidentate ligand), [Rh(mac)(CH3)] 2(μ-L') [L'= 4-cyanopyridine (4-CN-py) or 4,4'-bipyridine (4,4'-bipy)] have been synthesized and characterized. The structures of Rh(bpb)(CH3) (4-[tert]Bu-py) (4-[tert]Bupy = 4-tert-butylpyridine), Rh(bpb)(CH3) (PMe2Ph), and [Rh(TTP)(CH3)]2(μ-4-CN-py) have been determined by X-ray crystallography. The Rh(TTP)R (R = 5-norbornene-2-methyl) have been synthesized and the structure have been established by X-ray crystallography. Ring opening metathesis polymerization of Rh(TTP)R with Ru(=CHPh)(PCy3)2Cl2 leads to formation of a pentamer. Cis-Pt(L")2(CH3)2 (L"2 = (4-[tert]Bu-py)2, (SEt2)2, COD, dppf and (PMe3)2 have been synthesized. The structure of Pt(dppf)(CH3)2 have been determined by X-ray crystallography. The metal-carbon stretching frequencies for Rh(bpb)(CH3)L, Rh(por) (CH3)L, Ga(TTP)(CH3) and In(TTP)(CH3) have been determined by near infrared FT-Raman spectroscopy. It was found that the nature of L, the equatorial macrocyclic ligand, metal center and oxidation state of the metal center affect metal-carbon stretching frequency. For cis-Pt(L")2(CH3) 2 it was also found that the nature of L" has a pronounced influence on the Pt-C stretching frequency. The heterobimetallic dinitrogen complexes [M(por)(N2)Re(PMe2Ph) 4Cl][OTf] and [M(por)(N2)Re(Et2dtc)(PMe2Ph)3 [OTf] (M = Fe, Ru(NO), Cr; por = OEP, TTP; OTf = triflate) have been synthesized and characterized by IR and UV/VIS spectroscopy. The structure of [Fe(por)(N2) Re(PMe2Ph)4Cl] [OTf] has been established by X-ray crystallography. The Fe-N(N), Re-N, and N-N distances are 1.93(l), 1.832(l), and 1.17(1) Å, respectively; the Fe-N-N and Re-N-N angles being 170(1)° and 177(l)°, respectively. Heterobimetallic nitrido-bridged complexes, Ru(Et2dtc)(PPh3)2(CO)[NOs(TolS2)2] (Et2dtc = N,N-diethyldithiocarbamate; TolS2 = 3,4-toluenedithiolate( 2-) and Ru(Et2dtc)(PPh3)2(CO)[NOs(mnt)2] (mnt = maleonitriledithiolate(2-)), have been synthesized and characterized by X-ray crystallography. A series of heterotrimetallic mnt complexes of the type [Ru(Et2dtc)(PPh3)2(CO)]2 [M(mnt)2 (M = Ni, Pd, Pt, Cu) have been isolated and their formal potentials have been determined by cyclic voltammetry